Substituted dinitroanilines

ABSTRACT

NEW AND VALUABLE SUBSTITUTED DINITROANILINES HAVING A GOOD HERBICIDAL ACTION AND A PROCESS FOR CONTROLLING THE GROWTH OF UNWANTED PLANTS WITH THESE COMPOUNDS.

United States Patent O US. Cl. 260-349 4 Claims ABSTRACT OF THE DISCLOSURE New and valuable substituted dinitroanilines having a good herbicidal action and a process for controlling the growth of unwanted plants with these compounds.

The present invention relates to new and valuable substituted dinitroanilines having a good herbicidal action and the use of these compounds as herbicides.

It is known to use 4-trifiuoromethyl-2,6-dinitro-N,N-dipropylaniline as a herbicide. However, its action is not satisfactory.

We have now found that substituted dinitroanilines of the formula N O a where one of the radicals R and R denotes nitro and the other denotes methyl, trifluoromethyl or methylsulfonyl, R denotes bromoethyl, alkylthioalkyl (having up to 4 carbon atoms), azidoalkyl (preferably azidoethyl and 2-azidopropyl-1), acyloxyethyl or 2-acyloxypropyl (acetyl, propionyl, chloroacetyl, dichloroacetyl, trichloroacetyl, a-chloropropionyl, B-chloropropionyl, chlorocar- 'bonyl, carbomethoxy, carbethoxy, N-methylcarbamoyl, N-ethylcarbamoyl), R has the same meanings as R and may additionally denote hydrogen or linear or branched alkyl, alkenyl or alkynyl each having up to 4 carbon atoms, hydroxyethyl, Z-hydroxyrop-yl, alkoxyalkyl (methoxyethyl, ethoxyethyl, Z-methoxypropyl, 2-ethoxypropyl) cyanomethyl, cyanoethyl or chloroethyl, and R further denotes chloroethyl when R denotes hydrogen, have a good herbicidal action.

The action is particularly in evidence on millet species When the compounds are used preemergence and at application rates of 0.5 to 3 kg. per hectare. The active ingredients are suitable for controlling unwanted plants in crops such as soya beans, cotton or Indian corn.

The new active ingredients are yellow crystalline substances or non-distillable oils.

The new compounds are produced in accordance with the following equation:

where R and R have the meanings given above and R denotes hydroxyethyl or Z-hydroxypropyl, and R denotes the same radicals as R and additionally linear or branched alkyl, alkenyl or alkynyl each having up to 4 carbon atoms, alkoxyalkyl, cyanomethyl or cyanoethyl.

The compounds thus obtained may be reacted in conventional manner with halogenating agents (COCI SOCI SOBr PBr or acylating agents (acid chlorides, isocyanates) to give the products of the invention. Comice pounds in which R denotes azidoalkyl are expediently produced by exchanging the azido radical for a halogen atom.

The suitably substituted secondary amines may also be reacted direct to form the products of the invention in accordance with the above equation.

Starting materials and intermediates may be produced for instance by the processes of US. Pats. 2,257,093 and 3,227,734 and in accordance with Journal of the Chemical Society, London, 1949, 190, suppl.

EXAMPLE 1 N-methylthioethyl-N-hydroxyethyl-2,6-dinitro-4- trifluoromethylaniline 54 parts (by weight) of 2,6-dinitro-4-trifluoromethylchlorobenzene is dissolved in 250 parts of tetrahydrofuran or benzene; subsequently, a mixture of 28.4 parts of N- methylthioethylaminoethanol and 20.2 parts of triethylamine is slowly added, and the whole is stirred for 2 hours at 50 to 60 C. After the triethylammonium hydrochloride has been filtered 011, the filtrate is concentrated in vacuo and the residue recrystallized from ethanol. Melting point: 60 to 62 C.; yield: 96%.

EXAMPLE 2 N-methylthioethyl-N-chloroethyl-Z, 6-dinitro-4- I trifiuoromethylaniline 18.5 parts of the compound of Example 1 is dissolved in 100 parts of carbon tetrachloride or benzene; after a small amount of dimethylformamide or N-methylpyrrolidone has been added, 9 parts of thionyl chloride is slowly introduced at 10 to 15 C., and the whole stirred for 2 hours at room temperature and for a further 2 hours at 50 to 60 C. The excess thionyl chloride is distilled off with the solvent, the residue is taken up in carbon tetrachloride and washed with water. After concentration in vacuo, the crystalline product is obtained which is recrystallized from ethanol/ligroin. Melting point: 138 to 139 C.

EXAMPLE 3 N-propyl-N-B-azidoethyl-2,6-dinitro-4- methylsulfonylaniline 18.3 parts of N-n-propyl N p chloroethyl 2,6- dinitro 4 methyl-sulfonylaniline (M.P.: 115 to 117 0, prepared as under Example 2) and 3.6 parts of sodium azide are dissolved in parts of dimethylformamide and the mixture is stirred for 4 hours at 70 to C. After the reaction mixture has been cooled it is poured into ice water and the product extracted with methylene chloride. Refractive index of the end product: 11 =l.5800.

EXAMPLE 4 N-n-butyl-N- fl-chloroacetyloxy-n-propyl -2,6-

dinitro-4-trifluoromethylaniline 17.5 parts of N-n-butyl-N-B-hydroxy-n-propyl-2,6-dinitro-4-trifiuoromethylaniline (M.P. 75 to 77 0.; prepared as in Example 1) is dissolved in 50 parts of toluene; 9.0 parts of chloroacetyl chloride is then slowly introduced. The mixture is then first stirred for 12 hours at room temperature, and for a further 3 hours at 40 to 50 C. The filtrated solution is concentrated in vacuo and the residue recrystallized from ethanol/ligroin. Melting point: 84 to 86 C.

EXAMPLE 5 N-methoxyethyl-N-chloroacety1oxyethyl-2,6-dinitro- 4-methylaniline 22.5 parts of N-methoxyethyl-N-hydroxyethyl-2,6-dinitro-4-methylaniline (prepared as in Example 1 from 2,6-dinitro-4-methylchlorobenzene and N-methoxyethyl- EXAMPLE 6 N-allyI-N-chlo rocarbonyloxyethyl-2,6-dinitro-4- trifiuoromethylaniline 67 parts of N-allyl-N-hydroxyethyl 2,6 dinitro-4-trifiuoromethylaniline (prepared as in Example 1;

is dissolved in 100 parts of carbon tetrachloride; at room temperature phosgene is passed in, the temperature rising'to approximately 40 C. After the reaction has subsided, the mixture is stirred for minutes and subsequently concentrated; the residue is recrystallized from ethanol/ligroin. Melting point: 80 to 82 C.

EXAMPLE 7 N-methoxyethyl-N- (N-methylcarbamoyloxyethyl) 2,6-dinitro-4trifiuoromethylaniline 17.7 parts of N-rnethoxyethyl N hydroxyethyl-2,6- dinitro-4-trifioromethylaniiine (prepared as in Example 1; M.P.: to 37 C.) is dissolved in 50 parts of acetone; a few drops of triethylamine are added, and 3.1 parts of methyl isocyanate is introduced. The mixture is subsequently stirred for 3 hours at about C., the solvent is then distilled off, the residue is taken up in methylene chloride, and the solution is washed with water and again concentrated. A dark oil is obtained. n =1.5270.

EXAMPLE 8 M ethyl-fl- N-al lyl-N-Z, 6-dinitro-4-trifiuoromethylphenyl)-aminoethyl carbonate At 10 to 20 C., 5.7 parts of methyl chloroformate is added to a solution of 16.8 parts of N-allyl-N-hydroxyethyl-2,6-dinitro-4-trifiuoromethylaniline and 5 parts of triethylamine in parts of chloroform; the mixture is stirred for 2 hours at room temperature and for 1 hour at from 40 to 50 C. The solution is then washed with water and concentrated. A dark oil is obtained. n =1.5280.

EXAMPLE 9 N-n-propyl-N- (fi-bromoethyl -2,6-dinitro-4 methylsulfonylaniline At 20 to 25 C, 13.4 parts of thionyl bromide is added to a solution of 17.4 parts of N-n-propyl-N-hydroxyethyl 2,6 dinitro 4 methylsulfonylaniline (prepared as in Example 1; M.P.: 100 to 102 C.) and 1 part of dirnethyliormamide in 100 parts of carbon tetrachloride. The mixture is subsequently stirred for 6 hours at room temperature and for 4 hours at from 50 to C. The solution is concentrated (12 mm. Hg) and the residue obtained is recrystallized from ethanol/ ligroin. Melting point: 124 to 126 C.

The following compounds were prepared in the same way as in these examples:

The agents according to the invention may be used as solutions, emulsions, suspensions or dusts. The form of application depends entirely on the purpose for which the agents are being used; in any case it should ensure a fine distribution of the active ingredient.

For the preparation of solutions to be sprayed direct, hydrocarbons having boiling points higher than 150 C., e.g. tetrahydronaphthalene or alkylated naphthalenes, or organic liquids having boiling points higher than 150 C. and having one or more than one functional group, e.g. the keto group, the ether group, the ester or the amide group, this group or these groups being attached as substituent(s) to a hydrocarbon chain or being a component of a heterocyclic ring, may be used as spray liquids.

Aqueous formulations may be prepared from emulsion concentrates, pastes or Wettable powders by adding water. To prepare emulsions the ingredients as such or dissolved in a solvent may be homogenized in water or organic solvents by means cf wetting or dispersing agents, e.g. polyethylene oxide adducts. Concentrates which are suitable for dilution with water may be prepared from active ingredient, emulsifying or dispersing agent and possibly solvent.

Dusts may be prepared by mixing or grinding the active ingredients with a solid carrier, e.g. kieselguhr, talc, clay or fertilizers.

The following experiments demonstrate the biological action of the new compounds.

EXAMPLE In a greenhouse, loamy sandy soil was filled into pots and sown with Zea mays, Soia hispida, Gossypium hirsutum, Echinochloa crus-galli, Digitaria sanguinalz's, Setaria spec., Lolium perenne, Poa annua and Alopecurus myosuroides.

The soil prepared in this manner was then treated with 3 kg. per hectare of each of the following active ingredients, each amount being dispersed in 500 liters of water per hectare:

l CHI-C r-Na N02 (H) N-B-methoxyethyl-N-B-azidoethyl-2,6-dinitro-4- trifluoromethylaniline (-III) N-ethyl-N-B-azidoethyl-LG-dinitro-4-trifiuoromethylaniline and, for comparison,

( IV) 4-trifluoromethyl-2,6-dinitro-N,N-dipropylaniline.

After 3 weeks, I, II and III had, compared with IV, far

superior compatibility with the crop plants, combined with EXAMPLE 11 In a greenhouse, loamy sandy soil was filled into pots and sown with Zea mays, Gossypium hirsutum, Soja hispida, Poa trivialz's, Lolium multiflorum Echinochloa crus-galli, Digitaria sanguinalis and Setaria spec.

The soil was then treated with 3 kg. per hectare of each of the following active ingredients, each amount being dispersed in 500 liters of water per hectare:

II-CIH1 FaC- CHr-CHz-O-COCH2C1 (I) v N09 (II) N-fl-(methylcarbamoyloxy)-ethyl-2,6-dinitro-4- fluoromethylaniline (-HI) N-fl-(chloroacetoxy)-ethyl-2,6-dinitro-4-trifluoromethylaniline (IV) -N,N-bis-[5-7-(chloroacetoxy)-ethy1]-2,6-dinitro- 4-trifluoromethylaniline and, for comparison,

(V) 4-trifluoromethyl-2,6-dinitro-N,N-dipropylaniline.

After 3 weeks I, II, III and IV had, compared with V, superior compatibility with the crop plants combined with a good herbicidal action.

Active lngredient.

I II III IV Crop plants:

Zea mays 0 0 I 0 35 Gossypz'um hirsutum 0 0 0 0 6 Soja hispida 0 0 0 0 30 Unwanted plants:

Poo trivialis 95 80 75 75 Lolium multiflorum 90 75 70 7O 90 Echinochloa crux-gum. 90 80 75 75 95 Digitaria sanquinelis 85 75 70 70 90 Setaria spec 80 75 70 70 80 NOTE.0=N0 damage; 100= Complete destruction.

The action of the following compounds corresponds to that of I, II and HI:

N-propyl-N-fl-azidoethyl-2,6-dinitro-4-methylsulfonylaniline; N-fi-methylmeracaptoethyl-N-fi-(chloroacetoxy)- ethyl-2,6-dinitro-4-trifluoromethylaniline; 4methyl-2,6-dinitro-N-n-propyl-N-B-azidoethylaniline; 4-methyl-2,6-dinitro-N-n-propyl-N-B-(chloroacetoxy)- ethylaniline; 4-methylsulfonyl-2,6-dinitro-N-n-propyl-N-B-(methoxycarboxy)-ethylaniline; 4-trifluoromethyl-2,6-dinitro-N-propyl-N-fi- (chloroacetoxy)-propylaniline; 4-trifluoromethyl-2,fi-dinitro-N-propyl-N-fi- (N'-methylcarbamoyloxy)-propylaniline; N-propyl-N-fi-bromoethyl-Z,6-dinitro-4-methylsu1fonylaniline; N-B-methoxyethyl-N-fi-brornoethyl-Zfi-dinitro-4-trifluoromethylaniline.

EXAMPLE I2 90 parts by weight of the compound of Example 1 is mixed with 10 parts by weight of N-methyLa-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

EXAMPLE 13 20 parts by weight of the compound of Example 2 is dissolved in a mixture consisting of 80 parts by Weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 14 20 parts by weight of the compound of Example 3 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 15 20 parts by Weight of the compound of Example 4 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280 C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniform ly distributing it therein, an aqueous dispersion is obtained containing 002% by weight of the active ingreclient.

EXAMPLE 16 20 parts by weight of the compound of Example 5 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquid is obtained containing 0.1% by weight of the active ingredient.

EXAMPLE 1? 3 parts by weight of the compound of Example 6 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

EXAMPLE 18 30 parts by weight of the compound of Example 7 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of parafiin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

We claim: 1. A substituted dinitroaniline of the formula Bouton, A. J. et al.: C.A., vol. (1966), p. 201l9e.

HENRY R. JILES, Primary Examiner M. A. M. CROWDER, Assistant Examiner US. (:1. X.R. 4 24226 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 10 Dated Nonemben 1913 lnventofls) Kan] aha at 91 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1,, line 44, "2-hydroxyropyl" should read 2-.hydroxypropy1 Column 6, line an, "sanquinalis" should read sangu1nalis Column 6, line 65-66, l-fluoromethylaniline" should read t-trifluoromethylaniline Column 7, line :9, "sanquinalis" should read .sanguinalis Column 7, line 19, "methylmeraoaptoethyl" should read I methylmercapfcoethyl Signed and sealed this 29th day of October 1971+.

(SEAL) Attest:

McCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents FORM PO-105O (10-69) USCOMM-DC 60376-3 69 u.s. GOVERNMENT nmmms OFFICE l9 O'3I6-SJ4. 

